CN104884550B - Aqueous inkjet ink is with acrylic resin emulsion and uses its aqueous jet ink composition - Google Patents

Aqueous inkjet ink is with acrylic resin emulsion and uses its aqueous jet ink composition Download PDF

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CN104884550B
CN104884550B CN201380067969.4A CN201380067969A CN104884550B CN 104884550 B CN104884550 B CN 104884550B CN 201380067969 A CN201380067969 A CN 201380067969A CN 104884550 B CN104884550 B CN 104884550B
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monomer
acrylic resin
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aqueous
methyl
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CN104884550A (en
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松本明久
井上俊满
神田泰治
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Nippon Yakin Kogyo Co Ltd
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Chuo Rika Kogyo Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/34—Hot-melt inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Ink Jet (AREA)

Abstract

[problem] also shows that the also excellent aqueous jet ink composition of the ink characteristic such as high viscosity and glossiness to not used thickener, a kind of aqueous inkjet ink acrylic resin emulsion is provided, it is the aqueous inkjet ink acrylic resin emulsion containing the acrylic resin particle that acid number is 1~100mgKOH/g,1The H AB-crosslinked polymer times be 5ms under determine acrylic resin particle surface region in containing acidic-group monomer containing molar ratio (As) and acrylic resin particle entirety in containing acidic-group monomer containing the ratio between molar ratio (At) (As/At) be more than 9.

Description

Aqueous inkjet ink is with acrylic resin emulsion and uses its aqueous inkjet ink group Compound
Technical field
The present invention relates to the acrylic resin emulsion that can be usefully used as aqueous inkjet ink.
Background technology
Ink-jet recording is to pass through aqueous ink composition to induce the electric signal of the Pulse of Arbitrary form of heat or machinery, It is sprayed on matrix with the form of the drop for spraying from aperture.The response pulse, ink is injected from nozzle and forms drop, drop Advanced to the ad-hoc location on matrix surface.After being attached on surface, it is necessary to fully maintain position and the chi of the drop Image that is very little and forming appropriate resolution ratio, makes droplet drying afterwards, and is fully attached to matrix surface.
In recent years, due to the innovative progress of ink mist recording technology, so so far in photo, hectographic printing Ink-jet recording is also using in image record (printing) of the fine in field.If using high viscous ink, can obtain To apparent image, therefore the exploitation for possessing the ink-jet printer towards high-viscosity black head has been carried out, it is desirable to can Suitable for the above-mentioned high viscous ink towards high-viscosity black head.
As the aqueous ink jet ink used in ink jet ink, for example, have developed：Comprising aqueous vehicle, self-dispersing face Material, silicone-containing surfactant, the ink composition (patent document of the polymer with specific glass transition temperature (Tg) 1)；Including at least the ink composition (patent document 2) of polymer, glycerine, thickener and water.In addition, disclosed in patent document 2 The method for adjusting using thickener the viscosity of ink.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-22328 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-202030 publications
The content of the invention
Problems to be solved by the invention
However, the aqueous jet ink composition using resin emulsion such for patent document 1, as a rule viscosity It is low, it is impossible to be directly applied for towards high-viscosity black head.
In addition, in order to be applied to towards high-viscosity black head, for example as described in Patent Document 2, it is also considered that use thickening Agent improves the method for the viscosity of ink, although the aqueous jet ink composition that high viscosity has been carried out using thickener can be Used towards in high-viscosity black head, but have the problem of the black glossiness reduction after printing.
Therefore, in this context, the present invention is provided to not used thickener to also show that high viscosity and light The acrylic resin emulsion of the also excellent aqueous jet ink composition of the ink characteristic such as pool property.
The scheme for solving problem
Then, the present inventor etc. further investigate in view of the foregoing and repeatedly, as a result find：Third for containing in the emulsion The containing ratio containing acidic-group monomer in its particle surface region emulsion high is used for aqueous jet in olefin(e) acid resinoid particle During ink composition, high viscosity and the excellent ink of glossiness can be obtained.
That is, purport of the invention is related to a kind of aqueous inkjet ink acrylic resin emulsion, it is characterised in that its be containing There is the aqueous inkjet ink acrylic resin emulsion of the acrylic resin particle that acid number is 1~100mgKOH/g,1H is certainly Rotation diffusion time be 5ms under determine acrylic resin particle surface region in containing acidic-group monomer containing mole Contain the ratio between molar ratio (At) (As/ containing acidic-group monomer in ratio (As) and acrylic resin particle entirety At it is) more than 9.
In addition, in the present invention, also providing a kind of aqueous jet ink composition, it uses aqueous inkjet ink acrylic compounds tree Fat liquor, and then comprising pigment, solvent and wetting agent.
The effect of invention
For the aqueous jet ink composition using aqueous inkjet ink acrylic resin emulsion of the invention, viscosity It is high, can be used in towards high-viscosity black head, and the black characteristic such as gloss is also harmonious excellent well, therefore can be used for The image record of fine.
Brief description of the drawings
Fig. 1 is described in NMR spectra, Polymer Preprints Japan Vol.60, No.2,3086 (2011) The explanatory diagram of As assay methods.
Specific embodiment
Hereinafter, the present invention is explained.
It should be noted that (methyl) acrylic acid refers to acrylic or methacrylic acid, (methyl) acryloyl in the present invention Base refers to acryloyl group or methylacryloyl, and (methyl) acrylate refers to acrylate or methacrylate.
Acrylic resin emulsion of the invention is following aqueous inkjet ink acrylic resin emulsion：It is to contain acid It is worth the aqueous inkjet ink acrylic resin emulsion of the acrylic resin particle for 1~100mgKOH/g,1H spins are expanded Dissipate the time be 5ms under determine acrylic resin particle surface region in contain molar ratio containing acidic-group monomer (As) and in acrylic resin particle entirety containing acidic-group monomer containing the ratio between molar ratio (At) (As/At) be 9 More than.
First, said with the acrylic resin of acrylic resin emulsion to constituting aqueous inkjet ink of the invention It is bright.
＜ acrylic resins ＞
The acid number of aforesaid propylene acid resin is necessary for 1~100mgKOH/g, preferably 1~50mgKOH/g, particularly preferably It is 1~30mgKOH/g.
When above-mentioned acid number is too high, the water resistance using black film obtained from the emulsion comprising the acrylic resin has drop Low tendency, when too low, the stability of acrylic resin particle also has the tendency of reduction.
It should be noted that in order to acid number is set in above range, such as single group containing acidic groups described later can be adjusted The compounding amount of body.
And, in aforesaid propylene acid resin,1The H AB-crosslinked polymer times are the acrylic resin particle of measure under 5ms Surface region in containing acidic-group monomer containing molar ratio (As) and acrylic resin particle entirety in containing acid Property group monomer be necessary for more than 9, preferably 10~100 containing the ratio between molar ratio (At) (As/At), particularly preferably 11 ~80, more preferably 12~60, especially preferably 13~40.
This is because, when above-mentioned As/At is too low, the aqueous spray of use gained aqueous inkjet ink acrylic resin emulsion The viscosity of black ink composition has the tendency of step-down.
As it is above-mentioned1The H AB-crosslinked polymer times be 5ms under determine acrylic resin particle surface region in contain The scope containing molar ratio (As) of acidic-group monomer, preferably 1~100, particularly preferably 2~80, more preferably 10 ~60.
When the value of above-mentioned As is excessive, the resistance to of black film obtained from the emulsion comprising aforesaid propylene acid resin particle is used Aqueous to have the tendency of reduction, when too low, the stability of acrylic resin particle has the tendency of reduction.
As the model containing molar ratio (At) containing acidic-group monomer in aforesaid propylene acid resin particle entirety Enclose, preferably 0.1~11, particularly preferably 0.5~8, more preferably 1~5.
When the value of above-mentioned At is excessive, the resistance to of black film obtained from the emulsion comprising aforesaid propylene acid resin particle is used Aqueous to have the tendency of reduction, when too low, the stability of acrylic resin particle has the tendency of reduction.
As above-mentioned monomer containing acidic-group, for example, can enumerate：Carboxyl group-containing monomer, monomer containing sulfonic group, phosphorous acidic group Monomer etc., wherein, from being readily able to obtain thickening effect aspect, preferably carboxyl group-containing monomer.
Above-mentioned As (the acid monomers ratio of particle surface) and At (the overall acid monomers ratio of particle) can be by parsing NMR Spectrum is calculated.
For example in the case that acidic-group is carboxyl, carboxyl group-containing monomer exists13Carboxylic is shown in C spectrum, in 190~180ppm The resonance line of base, on the other hand, acrylate monomer exists13Carbonyl in C spectrum, in 180~170ppm shows ester structure Resonance line.Area ratio according to this 2 kinds of resonance lines can calculate respective copolymerization composition.
Herein, above-mentioned As refers to, as described above, NMR's1The H AB-crosslinked polymer times are the acrylic compounds of measure under 5ms The containing ratio containing acidic-group monomer in the surface region of resin particle.Herein, as problem it is as mensuration region Acrylic resin particle surface region, i.e. from the depth of particle surface, but on acrylic resin particle surface Certain depth can be calculated with the formula of following (mathematical expressions 1).
(mathematical expression 1)
L=0.816 × (τ d)1/2
(herein, above-mentioned L (nm) represents the depth from acrylic resin particle surface, and 0.816 represents coefficient, τ d (ms) Represent1H AB-crosslinked polymer time (bibliography：Masuda et al.,Solid State Nuclear Magnetic Resonance(2003)23,198)。〕
That is, according to the formula of above-mentioned (mathematical expression 1), NMR's in As1The H AB-crosslinked polymer times, 5ms caused from acrylic compounds The depth of resin particle surfaces about 1.8nm.That is, As is by calculating the depth about 1.8nm from acrylic resin particle surface In region containing acidic-group monomer containing obtained from molar ratio.
On the other hand, above-mentioned At refers to, in acrylic resin particle entirety containing acidic-group monomer containing mole Ratio, as described above, can be calculated by parsing NMR spectra.
As long as above-mentioned NMR spectra just can generally be determined for the NMR devices commonly used, for example, device can be determined by NMR The measure of (Bruker Corporation systems, AVANCE III 400WB) and obtain.And.Above-mentioned As can be by Fig. 1 institutes The method described in Polymer Preprints Japan Vol.60, No.2,3086 (2011) shown is determined, and above-mentioned At can With by using CP/MAS (cross polarization combination Magic angle spinning (Cross Polarization Magic Angle Spinning)) determine.
Each symbol on Fig. 1 proceeds as described below explanation (magnetic direction wherein, is set into z-axis).
·90±x：Make 90 ° of pulses successively towards x ,-x-axis rotatable phase.
·90-x：Make 90 ° of pulse direction-x-axis rotatable phases.
·180y：180 ° of pulses are rotated centered on y-axis.
·τt：The time that the magnetization of solid constituent disappears
·τd：1The H AB-crosslinked polymer times
·VACP：Polarization of reporting to the leadship after accomplishing a task (amplitude variable Magic angle spinning (Variable Amplitude Magic Angle Spinning)) part
·(i)：Time of contact (time needed for polarization of reporting to the leadship after accomplishing a task)
·DD：Decoupling (dipole decouples (Dipole Decoupling))
·PD：To the stand-by period (postponing (Post Delay) afterwards) of next pulse
·FID：Free damping (Free Induction Decay)
·(ii)：Obtain the time of FID signal
Hereinafter, the assay method to NMR spectra is specifically described.
The assay method ＞ of ＜ NMR spectras
NMR spectra (including As and At) determines device (Bruker Corporation systems, AVANCE III by NMR 400WB), at a temperature of 20 DEG C, using 4mm φ solid CP/MAS probes and 4mmHRMAS test tubes table 1 below measure bar It is measured under part.
[table 1]
For the average grain diameter of aforesaid propylene acid resin particle, preferably 40~300nm, particularly preferably 50~ 200nm, more preferably 60~150nm.
When above-mentioned average grain diameter is excessive, the glossiness of film has the tendency of reduction, when too small, must largely be used during manufacture Emulsifying agent, economically as inefficient tendency.
It should be noted that above-mentioned average grain diameter be use dynamic light scattering method (DLS), will be in 23 DEG C of temperature, angle of scattering Volume average particle size obtained from when the auto-correlation function determined under 90 ° carries out cumulant fitting (cumulant fitting). As measure device, it is possible to use " Nicomp 380 " of Particle Sizing Systems Inc..
Herein, the surface region of above-mentioned acrylic resin particle refers to, the volume overall relative to particle be about 3~ The surface region of 25% volume.
Acrylic resin with above-mentioned characteristic can be obtained by the polymerization of a step, it is also possible to more than two steps Polymerization and obtain, from by further improve after walk polymerization in containing acidic-group monomer compounding ratio such that it is able to promote Monomer containing acidic-group sets out in terms of the segregation of particle surface, is preferably obtained by polymerizations more than two steps.
In the case of the polymerization of an above-mentioned step, for example, by make the acid number of acrylic resin particle for 1~ The scope of 100mgKOH/g and substantially improve as the water miscible compounding ratio containing acidic-group monomer, such that it is able to promote The monomer makes the emulsion polymerization comprising desired acrylic resin particle to the segregation of particle surface.
In the case of the polymerization of above-mentioned two step (n is 2 situation), for example, following methods etc. can be enumerated：By the 1st step Monomer component after emulsion polymerization obtains the 1st emulsion, be added thereto to comprising more the 2nd steps containing acidic-group monomer Monomer component, emulsion polymerization is further carried out in the 1st emulsion.
Above-mentioned aggregation number n is more than 2 integer, preferably 2~3, particularly preferably 2.When n is excessive, also there is thickening to imitate The tendency that fruit reduces.
In the polymerization of aforesaid propylene acid resin, for the monomer composition in each polymerization procedure, following weights are preferably met Amount is than (α) and the relation of (β).
Make in being polymerized of the monomer containing acidic-group (1a) used in the polymerization of (α) the 1st step~the (n-1) step and the n-th step The weight ratio ((1a)/(2a)) of monomer containing acidic-group (2a) is 0/100~40/60.
Used in being polymerized of the total amount (X1) of the monomer used in the polymerization of (β) the 1st step~the (n-1) step and the n-th step The weight ratio ((X1)/(X2)) of the total amount (X2) of monomer is 99/1~60/40.
In above-mentioned (α), for the monomer containing acidic-group (1a) that is used in the polymerization of above-mentioned 1st step~the (n-1) step and The weight ratio ((1a)/(2a)) of the monomer containing acidic-group (2a) used in the polymerization of the n-th step, preferably (1a)/(2a)=0/ 100~40/60, (1a)/(2a)=0.5/99.5~20/80, particularly preferably (1a)/(2a)=1/99~10/ are more preferably 90。
Cannot fully be carried when (2a) is very few relative to the consumption of (1a), when forming ink jet ink composition and high-viscosity inclined To.
In addition, in above-mentioned (β), the total amount (X1) of the monomer for being used in the polymerization of above-mentioned 1st step~the (n-1) step, With the weight ratio ((X1)/(X2)) of the total amount (X2) of the monomer used in being polymerized of the n-th step, preferably (X1)/(X2)=99/1 ~60/40, (X1)/(X2)=99/1~80/20, particularly preferably (X1)/(X2)=98/2~90/10 are more preferably.
When above-mentioned (X2) is excessive relative to the content ratio of (X1), the viscosity of acrylic resin has to be become too high and inclines To when too low, having when ink-jet ink composition is made cannot fully put forward high-viscosity tendency.
It is described in detail when hereinafter, for manufacturing acrylic resin by n=2, i.e. two-stage polymerization.
First, in the polymerization of the 1st step, can make with monomer containing acidic-group (1a) and (methyl) acrylic ester monomer (1b) is polymerized as the monomer component [I] of main component.
In this specification, main component refers to account for overall more than half composition, is also only made up of main component including overall Situation.
As above-mentioned monomer containing acidic-group (1a), for example, can enumerate：It is carboxyl group-containing monomer, monomer containing sulfonic group, phosphorous Acid-based monomers etc., wherein, from thickening effect aspect, preferably carboxyl group-containing monomer can be readily obtained.
As above-mentioned carboxyl group-containing monomer, for example, can enumerate：(methyl) acrylic acid, acrylic acid dimer, butenoic acid, Malaysia Acid, maleic anhydride, fumaric acid, citraconic acid, glutaconate, itaconic acid, acryloyl amine-n-glycolic, cinnamic acid etc..Wherein, it is excellent Choosing (methyl) acrylic acid, from the stability aspect of ink-jet ink composition, particularly preferably methacrylic acid.
As above-mentioned monomer containing sulfonic group, for example, can enumerate：Vinyl sulfonic acid, 2- acrylamide-2-methyl propane sulfonics, Styrene sulfonic acid, allyl sulphonic acid, 3- sulfopropyls (methyl) acrylate, double-(3- sulfopropyls)-itaconate etc..
As above-mentioned phosphorous acid-based monomers, for example, can enumerate vinyl sulfonic acid etc..
When not using above-mentioned monomer containing acidic-group (1a), the black film from obtained from using aqueous jet ink composition Physical property (resistance to alcohol repellency, water resistance) excellent aspect is set out, and is preferred, during using above-mentioned monomer containing acidic-group (1a), as Content in monomer component [I], preferably 0.1~20 weight %, particularly preferably 0.5~10 weight %, more preferably 1~5 Weight %.
When the above-mentioned content containing acidic-group monomer is excessive, the thing of black film obtained from aqueous jet ink composition is used Property (resistance to alcohol repellency, water resistance) has the tendency of reduction.
As above-mentioned (methyl) acrylic ester monomer (1b), for example, can enumerate：(methyl) methyl acrylate, (methyl) Ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid n-propyl, (methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) n-octyl, propylene The different monooctyl ester of acid, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) propylene (methyl) alkyl acrylates such as sour stearyl ester, the different stearyl ester of (methyl) acrylic acid；(methyl) cyclohexyl acrylate, (methyl) third Alicyclic (methyl) acrylate such as olefin(e) acid isobornyl thiocyanoacetate etc..In the case of (methyl) alkyl acrylate, the carbon number of alkyl leads to Often it is 1~20, is particularly preferably 1~12, is more preferably 1~8.They can be used alone or combine two or more and use.
In above-mentioned (methyl) acrylic ester monomer (1b), it may be preferred to use methyl methacrylate, the positive fourth of acrylic acid Ester, the excellent aspect of the physical property (resistance to alcohol repellency, water resistance) of black film obtained from using aqueous jet ink composition, Particularly preferably methyl methacrylate.
As content of above-mentioned (methyl) the acrylic ester monomer (1b) in monomer component [I], preferably 80~100 weights Amount %, particularly preferably 90~99.9 weight %, more preferably 95~99.5 weight %, (methyl) acrylic ester monomer (1b) Content it is very few when, the physical property (resistance to alcohol repellency, water resistance) using black film obtained from aqueous jet ink composition has reduction Tendency.
In the present invention, can make as needed except monomer containing acidic-group (1a), (methyl) acrylic ester monomer Monomer (1c) copolymerization beyond (1b), for example, can enumerate following monomer (a)~(h) etc..
(a) hydroxyl ethylenically unsaturated monomer.
(b) ethylenically unsaturated monomer containing epoxy radicals.
(c) ethylenically unsaturated monomer containing methylol.
(d) ethylenically unsaturated monomer containing alkoxyalkyl.
(e) cyano-containing ethylenically unsaturated monomer.
F () has more than 2 ethylenically unsaturated monomers of free-radical polymerised double bond.
G () has the ethylenically unsaturated monomer of amino.
(h) ethylenically unsaturated monomer containing aromatic rings.
As the acrylic resin used in the present invention, in addition to above-mentioned (a)~(h), can also fit as needed When use propionate, tertiary ethylene carbonate, vinyl pyrrolidone, methyl vinyl ketone, butadiene, ethene, propylene, chlorine The monomers such as ethene, vinylidene chloride.
As above-mentioned hydroxyl ethylenically unsaturated monomer (a), for example, can enumerate：(methyl) Hydroxyethyl Acrylate, (first Base) (methyl) hydroxyalkyl acrylates such as hydroxypropyl acrylate, the polyalkylene two such as polyethylene glycol (methyl) acrylate Alcohol (methyl) acrylate etc., they can be used alone or in combination of two or more kinds.Wherein, it is however preferred to have carbon number 2~4 Hydroxy alkyl (methyl) hydroxyalkyl acrylates, the PAG (methyl) third of the alkylidene with carbon number 2~4 Olefin(e) acid ester, particularly preferably (methyl) Hydroxyethyl Acrylate.
As above-mentioned ethylenically unsaturated monomer containing epoxy radicals (b), for example, can enumerate：(methyl) glycidyl Ester, allyl glycidyl ether, (methyl) acrylic acid methylglycidyl esters etc., they can be used alone or combine 2 kinds with On use.Wherein, preferably (methyl) glycidyl acrylate.
As above-mentioned ethylenically unsaturated monomer containing methylol (c), for example, can enumerate：N- methylols (methyl) acryloyl Amine, dihydroxymethyl (methyl) acrylamide etc., they can be used alone or in combination of two or more kinds.
As above-mentioned ethylenically unsaturated monomer containing alkoxyalkyl (d), for example, can enumerate：N- methoxies (methyl) Acrylamide, N- butoxymethyls (methyl) acrylamide, methoxy ethyl (methyl) acrylate, methoxy-propyl (methyl) The alkoxyalkyls (methyl) such as acrylate, ethoxyethyl group (methyl) acrylate, ethoxycarbonyl propyl (methyl) acrylate Polyalkylene glycol mono alkoxy (methyl) acrylate such as acrylate, polyethylene glycol mono methoxy (methyl) acrylate Deng they can be used alone or in combination of two or more kinds.
As above-mentioned cyano-containing ethylenically unsaturated monomer (e), for example, can enumerate：(methyl) acrylonitrile etc..
There are more than 2 ethylenically unsaturated monomers (f) of free-radical polymerised double bond as above-mentioned, for example, can lift Go out：Divinylbenzene, polyoxyethylene two (methyl) acrylate, PPOX two (methyl) acrylate, neopentyl glycol two Two (methyl) acrylate, trimethylolpropane tris (methyl) such as (methyl) acrylate, butanediol two (methyl) acrylate Four (methyl) acrylate such as acrylate etc. three (methyl) acrylate, pentaerythrite four (methyl) acrylate etc., they Can be used alone or in combination of two or more kinds.
As the above-mentioned ethylenically unsaturated monomer (g) with amino, for example, can enumerate：N, N- dimethyl aminoethyl (methyl) acrylate, N, N- diethylaminos ethyl (methyl) acrylate etc., they can be used alone or combine 2 kinds with On use.
As above-mentioned ethylenically unsaturated monomer containing aromatic rings (h), for example, can enumerate：Styrene, AMS, (methyl) benzyl acrylate, (methyl) acrylate etc., they can be used alone or in combination of two or more kinds.
As in addition to above-mentioned (1a), (1b) also use monomer (1c) when monomer (1c) it is whole relative to monomer component [I] The content ratio of body, preferably 0~10 weight %, particularly preferably 0~5 weight %.List in addition to above-mentioned (1a), (1b) When the content ratio of body (1c) is excessive, the water resistance using black film obtained from aqueous jet ink composition has inclining for reduction To.
Then, in the polymerization of the 2nd step, can be added with monomer containing acidic-group in the polymer of above-mentioned 1st step (2a) and (methyl) acrylic ester monomer (2b) are polymerized as the monomer component [II] of main component.
As above-mentioned monomer containing acidic-group (2a), for example, can enumerate same with above-mentioned monomer containing acidic-group (1a) Material.Wherein, from the aspect that thickening power is excellent, preferably carboxyl group-containing monomer, particularly preferably (methyl) acrylic acid, More preferably methacrylic acid.
As content of the above-mentioned monomer containing acidic-group (2a) in monomer component [II], preferably 20~80 weight %, Particularly preferably 30~70 weight %, more preferably 40~60 weight %.
When the above-mentioned content containing acidic-group monomer is excessive, the thing of black film obtained from aqueous jet ink composition is used Property (resistance to alcohol repellency, water resistance) has the tendency of reduction, when very few, is difficult to obtain sufficient thickening effect.
As above-mentioned (methyl) acrylic ester monomer (2b), can enumerate and above-mentioned (methyl) acrylic ester monomer (1b) same material.Wherein, it is (resistance to alcohol repellency, water-fast from the physical property using black film obtained from aqueous jet ink composition Property) excellent aspect sets out, preferably (methyl) methyl acrylate, n-butyl acrylate, particularly preferably (methyl) acrylic acid Methyl esters, more preferably methyl methacrylate.
As content of above-mentioned (methyl) the acrylic ester monomer (2b) in monomer component [II], preferably 20~80 weights Amount %, particularly preferably 30~70 weight %, more preferably 40~60 weight %.
When the content of above-mentioned (methyl) acrylic ester monomer is excessive, it is difficult to obtain thickening effect, when very few, Have the tendency of to be easy to reduce using the physical property (resistance to alcohol repellency, water resistance) of black film obtained from aqueous jet ink composition.
In addition, as the monomer in addition to monomer containing acidic-group (2a), (methyl) acrylic ester monomer (2b) (2c), it is also possible to use the monomer same with above-mentioned monomer (1c) as needed.
As in addition to above-mentioned (2a), (2b) also use monomer (2c) when monomer (2c) it is whole relative to monomer component [II] The content ratio of body, preferably 0~10 weight %, particularly preferably 0~5 weight %.List in addition to above-mentioned (2a), (2b) When the content ratio of body (2c) is excessive, the water resistance of film has the tendency of reduction.
Then, it is polymerized respectively using above-mentioned monomer component [I] and [II], so as to obtain acrylic resin emulsion. First, acrylic resin emulsion is illustrated.
As the composition for obtaining aforesaid propylene acid resin emulsion, in addition to above-mentioned monomer component [I] and [II] Further preferably use surfactant, and then can suitably use as needed polymerization initiator, polymerization regulator, plasticizer, into The other compositions such as film auxiliary agent.
As above-mentioned surfactant, as long as using known general surfactant, such as can enumerate：It is cloudy from The reactive surfactant of subtype, cationic and nonionic, the non-reaction of anionic, cationic and nonionic Property surfactant.
Wherein, from the aspect that polymerization stability and ageing stability are excellent, anionic reactivity table is preferably used The non-reacted surfactant of face activating agent, anionic, the non-reacted surfactant of nonionic.
In addition, during using non-reacted surfactant, from the aspect that ageing stability is excellent, preferred compositions make With the non-reacted surfactant of anionic and the non-reacted surfactant of nonionic.
As above-mentioned anionic reactive surfactant, as long as being lived for anionic and with reactive surface Property agent, be not particularly limited, can for example enumerate with following formulas (1)~(11) like that structure surfactant.
Herein, in formula (1)~(11), R1It is alkyl, R2It is hydrogen or methyl, R3It is integer, m that alkylidene, n are more than 1 Integer with l is more than 1, there is the relation of " m+l=3 ".In addition, X is SO3NH4、SO3Any one of Na.
As above-mentioned anionic reactive surfactant, specifically, can enumerate：“Ade Gallia Soap SE-20N”、“Ade Gallia Soap SE-10N”、“Ade Gallia Soap PP-70”、“Ade Gallia Soap PP- 710 ", " Ade Gallia Soap SR-10 ", " Ade Gallia Soap SR-20 " (more than, Asahi Denka Kogyo K. K System), " Eleminol JS-2 ", " Eleminol RS-30 " (more than, Sanyo Chemical Industries, Ltd.'s system), " LATEMUL S- 180A ", " LATEMUL S-180 ", " LATEMUL PD-104 " (more than, Kao Corp's system), " Aqualon BC-05 ", “Aqualon BC-10”、“Aqualon BC-20”、“Aqualon HS-05”、“Aqualon HS-10”、“Aqualon HS- 20 ", " New Frontier S-510 ", " Aqualon KH-05 ", " Aqualon KH-10 " (more than, the first industrial pharmaceutical strain Formula commercial firm system), the commercially available product such as " Phosphanol TX " (Toho Chemical Industry Co., Ltd.'s system).
In above-mentioned anionic reactive surfactant, from acrylic acid reaction is good, emulsion intercalation method is good Aspect set out, particularly preferred above-mentioned formula (3), (4), (5), (9), the surfactant of structure shown in (10), do not have There is the anionic reactive emulsifier of alkyl phenol structure, specifically, preferably " Ade Gallia Soap SR-10 ", " Ade Gallia Soap SR-20”、“Eleminol JS-2”、“Eleminol RS-30”、“LATEMUL S-180A”、“LATEMUL S-180 ", " LATEMULPD-104 ", " Aqualon KH-05 ", " Aqualon KH-10 " etc..Wherein, more preferably " Aqualon KH-10”、“LATEMUL PD-104”。
As the non-reacted surfactant of above-mentioned anionic, for example, can enumerate：Alkyl sulfate, alkyl benzene sulphonate Salt, alkyl sulfonate, alkyl diphenyl base ether disulfonate, laureth sulfate, polyoxyethylene alkyl phosphate Deng.
As the non-reacted surfactant of above-mentioned nonionic, for example, can enumerate：Polyoxyethylene alkyl ether, polyoxy second Allylic alkylation phenyl ether, epoxy ethane-epoxy propane block polymer, sorbitan fatty acid esters, polyoxyethylene fatty acid Deng.
As above-mentioned nonionic reactive surfactant, for example, can enumerate X changes in above-mentioned formula (1)~(11) It is the surfactant of hydrogen, specifically, can enumerates：“Ade Gallia Soap NE-10”、“Ade Gallia Soap NE-20”、“Ade Gallia Soap NE-30”、“Ade Gallia Soap NE-40”、“Ade Gallia Soap ER- 10”、“Ade Gallia Soap ER-20”、“Ade Gallia Soap ER-30”、“Ade Gallia Soap ER-40” (more than, Asahi Denka Kogyo K. K's system), " Aqualon RN-10 ", " Aqualon RN-20 ", " Aqualon RN-30 ", Commercially available products such as " Aqualon RN-50 " (more than, Di-ichi Kogyo Seiyaku Co., Ltd.'s system).
It should be noted that above-mentioned surfactant can be compounded in the emulsified monomer liquid comprising monomer mixture, or Person can be previously added in for the polymeric kettle of polymerized monomer composition, or can also be applied in combination both.In addition, compounding table During the activating agent of face, not only can directly be compounded surfactant, surfactant can also be separately dissolved in solvent, monomer into It is compounded in point.And then, the compounding of surfactant can be used for any polymerization procedure, it is also possible to be compounded several times.
For the consumption of above-mentioned surfactant, relative to monomer component [I] and the weight portion of total 100 of [II], preferably It is 0.1~10 weight portion, particularly preferably 3~5 weight portions.
When above-mentioned surfactant is very few, polymerization stability has the tendency of reduction, and when excessive, Physical properties of coating film has inclining for reduction To.
As above-mentioned polymerization initiator, it is possible to use water-soluble, oil-soluble.Can for example enumerate：Alkyl peroxy Thing, tert-butyl hydroperoxide, cumene hydroperoxide, to methane hydroperoxides, lauroyl peroxide, 3,5,5- front threes Base caproyl peroxide, sim peroxides, tert-butyl cumyl peroxide, benzoyl peroxide, dichloro-benzenes first Acyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1- bis(t-butylperoxy) -3,3,5- front threes Butylcyclohexane, 3,3,5 trimethyl hexanone peroxide, methyl cyclohexanone peroxide, the carbonic acid of Di-Isobutyl peroxy two The organic peroxides such as ester, the carbonic ester of two -2- ethylhexyls peroxy two, t-butylperoxy isobutyl ester, 2,2 '-azo is double different Butyronitrile, dimethyl -2,2 '-azobisisobutylonitrile ester, 2,2 '-azo double (2,4- methyl pentane nitriles), double (the 2- methyl of 2,2 '-azo Butyronitrile), potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide, ammonium (amine) salt, 2 of the double -4- cyanopentanoic acids of 4,4 '-azo, Double (the 2- formyls amidoxime) dihydrochlorides of 2 '-azo, double (the 2- methylbutyryls amidoxime) hydroxides of dihydrochloride four of 2,2 '-azo Thing, 2,2 '-azo double { 2- methyl-N- (double (the hydroxymethyl) -2- hydroxyethyls of 1,1-)-propionamides }, the double (2- of 2,2 '-azo Methyl-N- (2- hydroxyethyls)-propionamide), various redox series catalysts are (now, as oxidant, it is possible to use over cure Sour ammonium, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, hydroperoxidation are withered Alkene, to methane hydroperoxides etc., as reducing agent, it is possible to use sodium sulfite, sodium acid sulfite, formaldehyde sulfoxylate hydrogen Sodium, ascorbic acid etc.) etc..
These polymerization initiators can be used alone or in combination of two or more kinds.Wherein, from the side that polymerization stability is excellent Face is set out, preferably potassium peroxydisulfate, sodium peroxydisulfate, redox series catalysts (oxidant：Potassium peroxydisulfate, sodium peroxydisulfate, reduction Agent：Sodium sulfite, sodium acid sulfite, rongalite, ascorbic acid) etc..
The consumption of above-mentioned polymerization initiator is preferably 0.01 relative to the weight portion of total 100 of monomer component [I] and [II] ~5 weight portions, particularly preferably 0.03~3 weight portion, more preferably 0.02~1 weight portion.The consumption of polymerization initiator is very few When, polymerization speed has the tendency of slack-off, when excessive, there is a molecular weight step-down of resulting polymers, and water resistance is easy to the tendency for reducing.
It should be noted that above-mentioned polymerization initiator can be previously added in polymeric kettle, or can also gather just Added before running the beginning jointly, or can also as needed in the additional compounding in polymerization midway.Or, can be pre- in monomer component [I] First it is compounded, or is compounded in the emulsion comprising above-mentioned monomer component [I].In addition, during compounding polymerization initiator, can gather Close initiator be separately dissolved in solvent, above-mentioned monomer component [I] and be compounded, or can be by lysed polymerization initiator Further form emulsification shape and be compounded.
In addition, as aforementioned polymeric conditioning agent, such as can enumerate：Chain-transferring agent, pH buffer etc..
As above-mentioned chain-transferring agent, for example, can enumerate：The alcohols such as methyl alcohol, ethanol, propyl alcohol, butanol；Acetaldehyde, propionic aldehyde, just The aldehydes such as butyraldehyde, furfural, benzaldehyde；The sulphur such as n-dodecane mercaptan, thioglycolic acid, thioglycolic acid monooctyl ester, thio glycerine Alcohols etc..They can be used alone or in combination of two or more kinds.
The use of the chain-transferring agent is effective from the aspect for carrying out with can making polymerization-stable, but has reduction propylene The degree of polymerization of acid resin, the possibility of the elastic modelling quantity of reduction gained film.Therefore, specifically, the consumption of chain-transferring agent 0.01~1 weight portion, particularly preferably 0.01~0.5 are preferably relative to the weight portion of total 100 of monomer component [I] and [II] Weight portion.When the consumption of above-mentioned chain-transferring agent is very few, there is deficiency as the effect of chain-transferring agent, when consumption is excessive, apply The elastic modelling quantity of film has the tendency of reduction.
In addition, as above-mentioned pH buffer, such as can enumerate：Soda ash (sodium carbonate), sodium acid carbonate, saleratus, Sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, sodium acetate, ammonium acetate, sodium formate, ammonium formate etc..They Can be used alone or in combination of two or more kinds.
The consumption of above-mentioned pH buffer is preferably 0.01 relative to the weight portion of total 100 of monomer component [I] and [II]~ 10 weight portions, particularly preferably 0.1~5 weight portion.When the consumption of above-mentioned pH buffer is very few, as the effect of polymerization regulator There is reduction, when consumption is excessive, have the tendency of easily to suppress reaction.
In addition, as foregoing plasticizer, such as can enumerate：Adipate ester system plasticizer, phthalic acid system plasticizer, Phosphate plasticizer etc., as foregoing coalescents, for example, can enumerate：Boiling point is more than 260 DEG C of coalescents.
As long as the consumption of above-mentioned plasticizer and coalescents does not hinder the purpose of the present invention just can suitably to select, for example, make It is plasticizer, relative to monomer component [I] and the weight portion of total 100 of [II], usually 0.1~50 weight portion, as film forming Auxiliary agent, relative to monomer component [I] and the weight portion of total 100 of [II], usually 0.1~50 weight portion.
In acrylic resin emulsion, dispersate is aforesaid propylene acid resin, and, as decentralized medium, preferably make Aforesaid propylene acid resin turns into the decentralized medium of dispersate.In such decentralized medium, more preferably comprising water-medium. Herein, water-medium refers to, water or contains the aqueous medium of alcohol solvent as main body with water, preferably water.
As the polymerization of acrylic resin emulsion, first, monomer component [I] is carried out into emulsion polymerization and obtains the 1st After emulsion, then monomer component [II] is added to the 1st emulsion, from the aspect that thickening power is excellent, carried out preferably wherein The method of emulsion polymerization.
As the method for the emulsion polymerization of above-mentioned monomer component [I], for example, can enumerate：To input water, table in reactor Face activating agent is simultaneously heated up, and the monomer dropping formula emulsion polymerization of monomer component [I] and polymerization initiator is added dropwise；With make drop Plus monomer component [I] mix monomer in advance with surfactant and water dispersion and emulsion after, the dispersion and emulsion list is added dropwise The emulsified monomer of body is added dropwise formula emulsion polymerization etc., the management, controlling from polymerization process such as polymerization temperatures it is excellent in terms of go out Hair, preferably emulsified monomer are added dropwise formula polymerization.
Above-mentioned emulsified monomer is added dropwise in formula emulsion polymerization, for example, can enumerate following methods：First, thrown in reactor Enter water, surfactant as needed, heated up after (usual 40~90 DEG C), emulsified with surfactant and water Dispersion, a part (usual 1~50 weight %) and polymerization initiator of gained monomer component [I] are compounded in the reactor, Implement initial polymerization (generally, the reaction time is 0.1~3 hour), then, remaining monomer component [I] is disposably compounded Or be compounded in a kettle. when being added dropwise, polymerization initiator is further compounded as needed, while being polymerized.
Monomer component [I] if polymerization since will monomer component [I] total amount compounding terminate moment generally continue to 0.5~2 hour (preferably 0.5~1 hour) be polymerized, so as to monomer component [I] aggregate rate more than 90% (preferably more than 95% ) moment completion polymerization, the 1st emulsion can be obtained, it is also possible to proceed the emulsion polymerization of monomer component [II].
Above-mentioned aggregate rate can be by the calculated value of nonvolatile component calculated by monomer composition and following nonvolatile components The ratio of measured value obtain.
(measured value of nonvolatile component)
A certain amount of emulsion is taken out to container, heating residual components when being dried 1 hour in 105 DEG C of baking oven are determined Weight.
The emulsion polymerization of above-mentioned monomer component [II] is preferably in the presence of the 1st emulsion, i.e. the polymerization of monomer component [I] is complete Into reactor in monomer component [II] is added dropwise.
The emulsion polymerization of above-mentioned monomer component [II] can by the total amount of monomer component [II] generally at 40~90 DEG C (preferably 60~85 DEG C) under disposably or be in batches compounded with 0.1~3 hour (preferably 0.5~2 hour).
More than, can be polymerized by 2 steps and obtain acrylic resin emulsion.
It should be noted that the situation of more than n=3, the polymerization for passing through more than 3 steps obtain acrylic resin emulsion In the case of, in order to complete present invention contemplates that purpose, can be as the polymerization of above-mentioned 2 step, using comparing in the polymerization of final step The method that other steps are polymerized using the monomer component containing acidic-group monomer comprising volume.
The aqueous inkjet ink of the invention with above-mentioned gained acrylic resin emulsion as main component can be obtained and use third Olefin(e) acid resin emulsion.
It should be noted that can suitably match somebody with somebody as needed in aqueous inkjet ink acrylic resin emulsion of the invention The additives such as mixed organic pigment, inorganic pigment, water-soluble additives, pH adjusting agent, preservative, defoamer, antioxidant.
Constitute the glass transition temperature of the acrylic resin of above-mentioned aqueous inkjet ink acrylic resin emulsion (Tg) it is preferably 0~120 DEG C, particularly preferably 30~100 DEG C, more preferably 40~100 DEG C.
When above-mentioned glass transition temperature is too high, film forming has the tendency of reduction, when too low, is combined using aqueous inkjet ink The physical property of black film is easily reduced obtained from thing.
It should be noted that above-mentioned glass transition temperature (Tg) can be based on (the transition temperatures of plastics of JIS K 7121 Assay method), determined with 10 DEG C/min of programming rate, 2nd run using Differential Scanning Calorimetry analysis meter (DSC).It is above-mentioned 2nd run refer to once to be warming up to more than glass transition temperature (1st run), by after certain thermal history, carrying out again Heat up (2nd run).
The solid component concentration of above-mentioned aqueous inkjet ink acrylic resin emulsion is preferably 20~50 weight %, especially Preferably 30~45 weight %.
When above-mentioned solid component concentration is too high, polymerization stability has the tendency of reduction, when too low, there is the free degree of ink formulations Narrow tendency.
The viscosity of above-mentioned aqueous inkjet ink acrylic resin emulsion be preferably 10~100000mPas, particularly preferably It is 10~50000mPas, more preferably 10~10000mPas.
When above-mentioned viscosity is too low, to having the tendency of that high-viscosity ink cannot be obtained after ink compounding, when too high, there is ink adjustment The tendency that operability is reduced.
It should be noted that above-mentioned viscosity is the value determined with Brookfield viscometer.
＜ aqueous jet ink compositions ＞
In the present invention, the appropriate compounding pigment dispersion in aqueous inkjet ink acrylic resin emulsion obtained above After body, solvent, wetting agent etc., with alkali process, such that it is able to obtain suitable aqueous jet ink composition.
As above-mentioned pigment dispersion, for example, can use Cabot Corporation systems, trade name " CAB-O-JET 200”、“CAB-O-JET 260M”、“CAB-O-JET 270Y”、“CAB-O-JET 400”、“CAB-O-JET 450C”、“CAB- O-JET 465M”、“CAB-O-JET 470Y”、“CAB-O-JET 480V”、“CAB-O-JET 554B”、“CAB-O-JET 740Y " etc., integrally 2~15 weight % can be generally used relative to aqueous jet ink composition.
As above-mentioned solvent, for example, can use ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol mono butyl base Ether, TC, triethylene glycol monobutyl base ether, propylene glycol monopropyl ether, tripropylene glycol monomethyl ether, 2- pyrrolidines Ketone, METHYLPYRROLIDONE, cyclohexyl pyrrolidone, 1- cyclohexyl -2-Pyrrolidone, oxazolidine -2- ketone, 1,3- diformazans Base -2- imidazolidinones etc., integrally 5~50 weight % can be generally used relative to aqueous jet ink composition.
As above-mentioned wetting agent, for example, can use Kyoeisha Chemical Co., Ltd.'s system, trade name " Polyflow KL- 245 ", the silicone based surfactants such as " Polyflow KL-260 ", Neos Corporation systems, trade name Fluorine system surfactants such as " Phthagent 100C ", " Phthagent 150CH " etc., it is whole relative to aqueous jet ink composition Body can generally use 0.01~1 weight %.
As by the method for the compoundings such as above-mentioned pigment dispersion, solvent, wetting agent, such as preferably in acrylic resin breast In liquid under agitation, addition dilute with water after each compounding ingredients (pigment dispersion, solvent, wetting agent etc.) method.
As the alkali used in above-mentioned alkali process, for example, can enumerate：The alkali metal containing such as NaOH salt, ammonia, alkanolamine Deng amine, from the physical properties excellent aspect using black film obtained from aqueous jet ink composition, preferably amine, spy You Xuanwei not ammonia.
For the condition of above-mentioned alkali process, for example, 5~10% are preferably added under agitation in aqueous jet ink composition The method of ammoniacal liquor.After addition terminates, a few minutes~a few houres are persistently stirred so as to complete to neutralize.
In addition, the compounding amount (solid constituent) of aqueous inkjet ink acrylic resin emulsion is relative to aqueous inkjet ink group Compound is integrally usually 1~20 weight %.
Aqueous jet ink composition can according to the printing process of known general ink jet type by coating base material so that Used as aqueous inkjet ink.
As above-mentioned base material, can enumerate：The nonabsorbable bases such as polyvinyl chloride, polyethylene terephthalate (PET) Absorbability base materials such as material, paper etc., wherein, preferably non-absorbability base material, particularly preferably polyvinyl chloride.
Aqueous inkjet ink acrylic resin emulsion of the invention is used as the water towards high-viscosity printing head Property ink-jet ink composition is useful.
Embodiment
Hereinafter, enumerate embodiment and further illustrate the present invention, but the present invention is just not limited to without departing from its purport Following embodiment.
It should be noted that " part ", " % " refer to weight basis in example.
Following average grain diameters is determined by above-mentioned method.
[embodiment 1]
The ＜ aqueous inkjet inks manufacture ＞ of acrylic resin emulsion (E1)
To being dissolved with 3.5 parts of non-reacted surfactant (2 parts of Kao Corp's system, trade name in 40 parts of water " EMULGEN 1135S-70 " (the non-reacted surfactant of nonionic), 1.5 parts of Clariant company systems, trade name " Emulsogen EPA073 " (the non-reacted surfactant of anionic)) the aqueous solution in add comprising metering system The monomer component [I] of 95 parts of sour methyl esters, 5 parts of butyl acrylate, is stirred, so as to make emulsified monomer composition.
Then, reacted to the glass system for possessing thermometer, mixer, reflux condensing tube, nitrogen ingress pipe and dropping funel 173 parts of water, 1 part of (Clariant company system of non-reacted surfactant are put into container；Trade name " Emulsogen EPA073 " (the non-reacted surfactant of anionic)), being stirred dissolves it, is warming up to 73 DEG C.Thereto in input State the 5% of emulsified monomer and stir, 1.3 parts of 3% potassium peroxydisulfate of addition carries out initial polymerization.Afterwards, keeping temperature is 80 DEG C, side With the above-mentioned emulsified monomer composition that 5.3 parts of 3% potassium peroxydisulfate and residual is added dropwise for 30 minutes 3 hours, while carrying out polymerisation.Drop Plus after terminating, the reaction of 60 minutes is carried out, terminate the polymerization of the 1st step.
Then, by comprising 2.8 parts of methyl methacrylate, the monomer component [II] of 2.4 parts of methacrylic acid and 3% over cure 0.87 part of sour potassium is added simultaneously, starts the polymerization of the 2nd step.It is ripe after pH is adjusted into 6 using 5% ammonia spirit after completion of dropwise addition Change reaction 1 hour.Afterwards, 50 DEG C are cooled to, and then are persistently stirred 1 hour.After being then cooled to room temperature, preservative is added (Thorjapan Co. Ltd. systems；Trade name " Acticide MBS ") 0.5 part, obtain milky aqueous inkjet ink propylene Acid resin emulsion (E1) (solid component concentration 30%, average grain diameter 70nm, resinous acid value 14mgKOH/g, glass transition temperature 95 DEG C of degree).
[comparative example 1]
The ＜ aqueous inkjet inks manufacture ＞ of acrylic resin emulsion (E1 ')
To being dissolved with 3 parts of reactive surfactant (1 part of Asahi Denka Co., Ltd.'s system, trade name " Ade in 36 parts of water Gallia Soap SR-10 " (anionic reactive surfactant), 2 parts of Di-ichi Kogyo Seiyaku Co., Ltd.'s system, commodity Name " Aqualon KH-10 " (anionic reactive surfactant)) the aqueous solution in add comprising methacrylic acid 85 parts of methyl esters, 15 parts of butyl acrylate, the monomer component of 2.2 parts of methacrylic acid, are stirred, so as to make emulsified monomer group Compound.
Then, reacted to the glass system for possessing thermometer, mixer, reflux condensing tube, nitrogen ingress pipe and dropping funel 80 parts of water, 1 part of (Asahi Denka Co., Ltd.'s system of reactive surfactant are put into container；Trade name " Ade Gallia Soap SR-10 "), being stirred dissolves it, is warming up to 73 DEG C.The 5% of above-mentioned emulsified monomer is put into thereto and is stirred, addition 3% 2.2 parts of potassium peroxydisulfate carries out initial polymerization.Afterwards, temperature is remained 80 DEG C, side was added dropwise 4.4 parts of 3% potassium peroxydisulfate with 4 hours With remaining above-mentioned emulsified monomer composition, while carrying out polymerisation.After completion of dropwise addition, using 10% ammonia spirit, pH is adjusted Whole is slaking reaction 1 hour after 6.
Afterwards, 50 DEG C are cooled to, and then are persistently stirred 1 hour.After continuing cool to room temperature, preservative is added (Clariant company systems；Trade name " NIPACIDE BIT 20 ") 0.5 part, obtain milky aqueous inkjet ink acrylic acid Resin emulsion (E1 ') (solid component concentration 41%, average grain diameter 105nm, resinous acid value 12mgKOH/g, glass transition temperature 80 DEG C of degree).
Using above-mentioned gained embodiment 1 and the aqueous inkjet ink acrylic resin emulsion of comparative example 1, carried out Ru following Determine.
The assay method ＞ of ＜ NMR spectras
NMR spectra (including As and At) is to determine device (Bruker Corporation systems, AVANCE III using NMR 400WB), it is measured at a temperature of 20 DEG C, using 4mm φ solid CP/MAS probes and 4mmHRMAS test tubes.Need Bright, condition determination is carried out as described in table 2 below.
[table 2]
Calculation method ＞s containing molar ratio of the ＜ containing acidic-group monomer
Containing being calculated as follows containing molar ratio for acidic-group monomer：For determining the spectrum for obtaining by above-mentioned NMR, use Following 186.5~181.8ppm of interval and 181.8~171.8ppm separates, and integrated value A and B are calculated by respective area ratio, It is applied to the formula of following (mathematical expressions 2), molar ratio is contained containing acidic-group monomer so as to calculate.
The CO (186.5~181.8ppm) of integrated value A ... methacrylic acids
The CO (181.8~171.8ppm) of integrated value B ... methyl methacrylates+butyl acrylate
(mathematical expression 2)
Methacrylic acid contains molar ratio (mole %)=100 × A/ (A+B)
Determined by above-mentioned NMR and calculate acrylic resin containing molar ratio calculation method containing acidic-group monomer The molar ratio of monomer containing acidic-group in emulsion (E1) and (E1 '), i.e. methacrylic acid, by gained As, At and " As/At " It is shown in Table 3 below.
[table 3]
Then, using above-mentioned gained acrylic resin emulsion (E1), (E1 '), aqueous jet ink composition is manufactured.
The manufacture ＞ of ＜ aqueous jets ink composition (C1)
Relative in embodiment 1 gained aqueous inkjet ink 9 parts of acrylic resin emulsion (E1) (solid constituent amount), Stirring is lower to be compounded as 10 parts of the 2-Pyrrolidone and 10 parts of propylene glycol monopropyl ether, wetting agent (Evonik Tego of coalescents Company system, Wet 260) 0.5 part, 70.5 parts of water, then using 10% ammoniacal liquor, pH is adjusted to 7.8, obtain aqueous inkjet ink group Compound (C1).
The manufacture ＞ of ＜ aqueous jets ink composition (C1 ')
Relative to gained aqueous inkjet ink 9 parts of acrylic resin emulsion (E1 ') (solid constituent amount) in comparative example 1, It is compounded under agitation as 10 parts of the 2-Pyrrolidone and 10 parts of propylene glycol monopropyl ether, wetting agent (Evonik of coalescents Tego company systems, Wet 260) 0.5 part, 70.5 parts of water, then using 10% ammoniacal liquor, pH is adjusted to 7.8, obtain aqueous jet Ink composition (C1 ').
＜ viscosity evaluates ＞
Using Brookfield viscometer (Toki Sangyo Co., Ltd.'s system, TVB10,23 DEG C, rotor No.1, rotating speed 60rpm), determine The viscosity of aqueous jet ink composition (C1) and (C1 ').Measurement result is shown in table described later 4.
It should be noted that the proper viscosity of aqueous jet ink composition is 4~30mPas or so, wherein, will The situation of more than 10mPas is considered as high-viscosity aqueous jet ink composition.Herein, above-mentioned gained aqueous jet ink composition (C1 ') is that outside proper viscosity scope, therefore cannot suitably be coated using bar coater.Therefore, in order that the aqueous inkjet ink group The viscosity of compound (C1 ') is compounded thickener for proper viscosity.
The manufacture ＞ of ＜ aqueous jets ink composition (C2 ')
Compounding is 10 weights relative to aqueous jet ink composition (C1 ') total amount in aqueous jet ink composition (C1 ') Measure thickener (Toho Chemical Industry Co., Ltd.'s system of %：Bismol YK-1), obtain same with aqueous jet ink composition (C1) Isoviscous ink composition, i.e. aqueous jet ink composition (C2 ').
For above-mentioned gained aqueous jet ink composition (C1) and (C2 '), glossiness is evaluated as described below.
＜ glossinesses evaluate ＞
Using bar coater No.4 (9.1 μm of wet (wet) (micron) is thick), aqueous jet ink composition (C1) and (C2 ') are applied It is overlying on polyvinyl chloride (PVC) piece (Metamark company systems, MD5).Afterwards, be put into 20 minutes in 100 DEG C of baking oven, make its into Film/drying, obtains coated side.
For gained coated side, gloss meter (BYK Gardner company systems are used：" Micro-TRI-gloss4520 "), survey Fixed 20 ° of gloss and 60 ° of gloss.
Metewand is as described below, show the result in table 4 below.
It should be noted that be 70 (△) as 20 ° of gloss of the glossiness of the PVC pieces of substrate sheets, 60 ° of gloss be 90 (○)。
(evaluation)
Zero ... glossiness more than 80.
△ ... glossiness more than 40~be less than 80.
× ... glossiness 0~be less than 40.
[table 4]
It can be seen from result according to above-mentioned table 4, the aqueous inkjet ink of embodiment 1 is with acrylic resin emulsion (E1) final In the polymerization of step compared with other steps, it is polymerized using comprising the further amounts of monomer component containing acidic-group monomer, from And the face side of acrylic resin particle is changed into high acid value, the high acid value composition dissolving on above-mentioned surface, between emulsion particle Interaction enhanced, therefore high viscosity, and then the spray obtained by said composition can be turned into when being made aqueous jet ink composition The glossiness of Mo Mo is also excellent.
On the other hand understand, the aqueous inkjet ink of comparative example 1 is made aqueous inkjet ink with acrylic resin emulsion (E1 ') Viscosity during composition (C1 ') is low, even if making above-mentioned aqueous jet ink composition high viscosity, such as aqueous jet using thickener Like that, the glossiness of ink jet ink is also deteriorated ink composition (C2 ').
It should be noted that in above-described embodiment, the specific scheme in the present invention is shown, but above-described embodiment is not It is simple example to cross, and being not construed as limiting property is explained.Certainly for obvious various modifications for those skilled in the art in this hair In bright scope.
Industrial applicability
When aqueous inkjet ink acrylic resin emulsion of the invention is used as aqueous jet ink composition, do not use Thickener also shows that high viscosity, and can obtain the also excellent effect of the ink characteristic such as glossiness, therefore as towards high viscosity The aqueous jet ink composition of printing head be particularly useful.

Claims (4)

1. a kind of aqueous inkjet ink acrylic resin emulsion, it is characterised in that it containing acid number is 1~100mgKOH/g that it is Acrylic resin particle aqueous inkjet ink acrylic resin emulsion,
1The H AB-crosslinked polymer times are the monomer containing acidic-group in the surface region of the acrylic resin particle determined under 5ms Containing molar ratio (As) and acrylic resin particle entirety in contain molar ratio (At) containing acidic-group monomer The ratio between (As/At) be more than 9, and the aqueous inkjet ink acrylic resin emulsion be by n walk polymerization and obtain , it possesses following weight ratio (α) and (β), wherein, n is more than 2 integer,
Used in being polymerized of the monomer containing acidic-group (1a) used in the polymerization of (α) the 1st step~the (n-1) step and the n-th step The weight ratio of monomer containing acidic-group (2a) is (1a)/(2a)=0/100~40/60；
Used in being polymerized of the total amount (X1) of the monomer [I] used in the polymerization of (β) the 1st step~the (n-1) step and the n-th step The weight ratio of the total amount (X2) of monomer [II] is (X1)/(X2)=99/1~60/40, described containing acidity in the monomer [II] The content of group monomer (2a) is 20~80 weight %.
2. aqueous inkjet ink acrylic resin emulsion according to claim 1, it is characterised in that the acrylic compounds The average grain diameter of resin particle is 40~300nm.
3. a kind of aqueous jet ink composition, it is characterised in that it contains：Aqueous inkjet ink described in claim 1 or 2 uses third Olefin(e) acid resin emulsion, pigment, solvent and wetting agent.
4. a kind of aqueous jet ink composition, it is characterised in that it is to use the aqueous jet ink composition described in claim 3 Obtained from alkali is processed.
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